Charles alexander



lUNlTED stares PATENT CHARLES ALEXANDER MARTIUS, OF BERLIN, G-ERIYIAN'Y.

PRODUCTlON OF WHXED AZQ COLURlhiG Wl/QTTEER.

foruing part of Letters Patent No. 358,865, dated March 8, 1887.

Application tiled March 17, 1886. Serial No. 195,592. (No specimens.) Patented in Germany January 26,1886,'No. 1,299; in England February 1:7, 18%(3, No. 2,2!3, and in France May 1, 11 86, No. 160,722.

To aZZ whom it may concern.-

Be it known that 1, CHARLES ALEXANDER MARTIUS, director of the Actiengesellschat't fiir Anilil'ifabrikation, of Berlin, in the Ki ugdom of Prussia, German Empire, have invented new and useful Improvements in the Production of Mixed Azo Colors; and I do hereby declare that the following is a full, clear, and exact description thereof, which will enable others skilled in the art to which it appertains to make and use the same.

I have found that the solutions of salts of tetrazodiphenyl or tetrazoditolyl in acting upon amines or phenols or sulpho-acids or carbo-acids, even when these substances are in excess, react in such manner that at iirst only one molecule of the tetrazo compound combines with one molecule of the amine, phenol, sulpho-acid, or carbo-acid. The first product obtained in such a way, containing still one free diazo group, is able to be combined again with the same or another amine, phenol, sulpho-acid, or carbo-acid, forming in this way a new azo color. A great variety olsimple and mixed azo colors may be prod need from the tetrazo compounds mentioned above.

The results of this invention show that the salts of the tetrazodiphenyl or tetrazoditolyl can give simple or mixed azo colors with the following classes of compounds:

1. Amines: (0,) primary amines, like ani' line, toluidine, Xylidine, alpha -i'1aphthylamine, beta-naphthylamine,benzidinc, tolidine, amidoazobcnzol, amidoazotoluol, &c.; (b,)secondary amines, like diphenylaminc, monomethylaniline, monoethylauiline; (0,) tertiary amines, like dimethylaniline, diethylaniline.

2. Sulpho acids of amines mentioned, sub. 1, as sulphanilie acid, naphthylamine-sulphoacid, dimethylaniline-sulpho-acid.

3. Garbo-acids oftbeamines mentioned, sub. 1, as amidobenzoic acid, amidotoluol acid.

4. Phenol, as carbolic acid, cresol, alpha- -naphthol, beta-naphthol, rcsorcine.

5. Phenol sulpho'acids,sulpho earboli 0 acid, alpha naphth ol sulpho-acid, beta naphtholmonosulpho acid, beta naphthol disulphoacid.

6. Phenol-carbo-acids, as salicylic acid, alpha-oxynaphthol acid, beta-oxynaphtoic acid.

The general process for producing such mixed azo colors consists in combining at firstone molecule of the tetrazo compound with one molecule of the substances mentioned, sub. 1, down to 6, and combining this intermediate product further with one molecule of' any one of the substances belonging to these six classes.

Simple colors-i. 0., such colors obtained by combining one molecule of tetrazo-compound with two molecules of the same substance of the six classes mentioned aboveare already known and have been patented. To this class belong the colors known in commerce as congo, benzopurpurino, and chrysamine. I have already patented a process for the production of mixed azo colors from salts of tetrazodiphcnyl and tetrazoditolyl, which con sists in reacting with theinterinediatc product formed by the combination of one of these salts with an amine or an amido-sulphoacid, a phenol, or a phcnol-sulphoacid upon another amine or amidosulpho-acid. This patent refers to those combinations mentioned above,

yet not patented.

The following exam plcs may explain my process:

1. BcnzuZine-lalpha-1211197117101 sa7ph0c01+ alpha amp/1 Utylmm'ne suZpJzo acid.18 kilos of benzidine are converted in the well-known manner into the tetrazo compound. The solution of the same is poured into a sol ution of 24.6 kilos of alphanaphthol-monosulpho-acid and 32 kilos of acetate of soda. It", now, a solution of 24.5 kilos of dry alphanaphthylamine -sulphonate of soda in one hundred liters of water is added and the mixture stirred for a longer period, an azo color is formed which dyes cotton a bro wn-violet shade.

2. J36IlE/itl'ilt6-ll)6liCt-7Z(QJ7LZOZ- clisahi/lo-acid, R +bcta-mqflithylammc suhllto acidr llliis color is obtained in the same manner as that described, sub. 1. 18.4. kilos of benzidiue are added to 34.8 kilos of beta-naphthol-disulphonate of soda (It-salt) and 24.5 kilos of beta-naphthylamine sulphonate of soda.

3. Total inc!-aQJhe-ntqfltlhol-sahflto-acid+betaaapht/zoldisuhflwwwid R.-The tolidine acts in a quite analogous manner as the benzidine. 21.2 kilos of tolidine, 24.6 kilos of alpha-naphthol-monosulphonate of soda, and Ell-.8kilos of betanaphthol disulphonate of soda (It) have to be used.

' kilos of sulphanilate of soda.

4. Tolidine-HtZpM naphthol disulpho ccid+ beta-naphthol. The naphthol disulpho-acid(R) inthe example 3 can be replaced by the equivalent quantity of beta-naphthol, 14.4 kilos.

5. 18.4 kilos of benzidine are converted with muriatic acid and nitrite of soda into the chloride of tetrazodiphenyl and mixed in presence of acetate of soda with a solution of 19.5

A color is obtained which in an alkaline soap bath dyes directly a yellow on cotton.

The process in the example 1 may be also reversed by acting at first with chloride of tetra-zodiphenyl upon salicylate of soda and afterward upon sulphanilate of soda.

In the examples 1 and 2 the sulphanilic acid or the salicylic acid may be replaced by the equivalent quantities of amido-benzoic acid.

zodixylyl and one molecule of an amine amidoo sulpho-acid, amido-carbo-acid,phenol,phenolsulpho acid, or phenol-carbo-acid, as set.forth.

CHARLES ALEXANDER lllAR'lIUS. \Vitnesses:

JOHN IMRIE, CHARLES M. WERLE. 

